CN113788946A - Preparation method and application of hydrophobic shape-controllable polysilsesquioxane - Google Patents

Preparation method and application of hydrophobic shape-controllable polysilsesquioxane Download PDF

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CN113788946A
CN113788946A CN202111185265.XA CN202111185265A CN113788946A CN 113788946 A CN113788946 A CN 113788946A CN 202111185265 A CN202111185265 A CN 202111185265A CN 113788946 A CN113788946 A CN 113788946A
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polysilsesquioxane
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CN113788946B (en
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马鹏程
李蒙
邢丹
郝斌
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract

The invention discloses a preparation method and application of hydrophobic shape-controllable polysilsesquioxane. The method adopts two silanes with different alkyl chains as reactants, and the polysilsesquioxane with controllable shape can be obtained in one step by simple ultrasonic oscillation after hydrolysis condensation reaction under the catalysis of alkali. The rod-shaped, cluster-shaped, three-dimensional sheet-shaped, porous, spherical and blocky appearance of the polysilsesquioxane can be regulated and controlled by regulating the content of reactants and the concentration of alkali, and the surface roughness of the polysilsesquioxane is changed, so that the hydrophobicity of the polysilsesquioxane is regulated and controlled. The polysilsesquioxane with the controllable shape is coated on the substrate made of different materials in a spinning mode, so that the wetting performance of the substrate can be improved, the obtained material can be applied to the field of hydrophobic coatings, and the polysilsesquioxane self-cleaning anticorrosion paint has the self-cleaning and anticorrosion functions. The preparation method provided by the invention is synthesized in one step, controllable in conditions, simple to operate and suitable for large-scale preparation and application.

Description

Preparation method and application of hydrophobic shape-controllable polysilsesquioxane
Technical Field
The invention relates to a preparation method and application of hydrophobic shape-controllable polysilsesquioxane, in particular to the technical field of synthesis of polysilsesquioxane.
Background
Polysilsesquioxane is a silicon-based organic/inorganic hybrid material with a molecular general formula of (RSiO)1.5) n (wherein n is an even number) takes a siloxane bond (Si-O-Si) as a main chain, and takes methyl, vinyl, aminopropyl phenyl, epoxy phenyl, long-chain alkyl and other groups as side chains, so that the organic polymer material has good organic solvent compatibility, biocompatibility and polymer compatibility. Polysilsesquioxane skillfully combines addition polymerization and polycondensation reactions in inorganic chemistry and high polymer chemistry, and the formed hybrid material has the performance which is not possessed by a simple organic matter or an inorganic matter, and the performance of the hybrid material is between that of the traditional organic material and the inorganic material, so that the hybrid material not only has excellent processability, toughness and low cost of the organic material, but also retains the heat resistance, oxidation resistance and excellent mechanical properties of the inorganic material. Polysilsesquioxanes have attracted considerable academic and industrial attention in recent years due to their excellent flame retardant properties, good stability to heat, weather and chemicals. At present, polysilsesquioxane has been widely used in the fields of luminescent materials, dielectric materials, liquid crystal materials, biomedical materials, heat-resistant flame-retardant materials, catalysts, and the like.
Polysilsesquioxanes of different structural types may be synthesized using silane reactants containing different amounts of alkoxy groups, as trifunctional monomers (RSi (OR')3Or RSiCl3) The product prepared by hydrolysis and condensation of the raw materials has a T-shaped structure; with a tetrafunctional monomer (Si (OR')4) The product prepared from the raw material has a Q-type structure. In the T-type structure, when siloxane containing alkyl chains or functional groups with different lengths is used as a reactant, the prepared polysilsesquioxane presents spherical and cubic morphologies. The synthesized polysilsesquioxane may be used as a hydrophobic material or a hydrophobic coating due to its high surface roughness, and may also be used as an electroluminescent and flame retardant material. ToThe preparation method of the polysilsesquioxane comprises a sol-gel method, a liquid phase deposition method, an emulsion method and the like, and particularly relates to the preparation of the hydrophobic material, the process is complex, industrial production cannot be carried out, and the practical application of the material is limited.
In view of the above, the invention provides a preparation method and application of polysilsesquioxane with controllable hydrophobic shape, which can synthesize polysilsesquioxane with controllable shape and hydrophobic property by adopting a simple one-step method through regulating the content of reactants and the concentration of alkali.
Disclosure of Invention
The invention aims to provide a preparation method and application of polysilsesquioxane with controllable hydrophobic shape. The method adopts two silanes with different alkyl chains as reactants, and the polysilsesquioxane with controllable shape can be obtained in one step by simple ultrasonic oscillation after hydrolysis condensation reaction under the catalysis of alkali. The rod-shaped, cluster-shaped, three-dimensional sheet-shaped, porous, spherical and blocky appearance of the polysilsesquioxane can be regulated and controlled by regulating the content of reactants and the concentration of alkali, and the surface roughness of the polysilsesquioxane is changed, so that the hydrophobicity of the polysilsesquioxane is regulated and controlled. The polysilsesquioxane with the controllable shape is coated on the substrate made of different materials in a spinning mode, so that the wetting performance of the substrate can be improved, the obtained material can be applied to the field of hydrophobic coatings, and the polysilsesquioxane self-cleaning anticorrosion paint has the self-cleaning and anticorrosion functions. The preparation method has the advantages of one-step synthesis, controllable conditions, simple operation and suitability for large-scale preparation and application.
The preparation method of the polysilsesquioxane with the controllable hydrophobic shape, disclosed by the invention, is carried out according to the following steps:
a. adding 50mL of ethanol into 4mL of NaOH solution with the concentration of 0.02-0.5M, mixing and stirring uniformly, and adding 0.5-8mL of long-chain silane and short-chain silane with the mass ratio of 1:0.1-10 to obtain a semitransparent solution, wherein the long-chain silane comprises hexadecyl trimethoxy silane or octadecyl trimethoxy silane; short chain silanes include methyltrimethoxysilane, vinyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, or dodecyltrimethoxysilane;
b. b, performing ultrasonic treatment on the semitransparent solution obtained in the step a for 1-10min at room temperature to obtain an opaque solution;
c. and c, standing and volatilizing the opaque solution obtained in the step b at room temperature for 1-14 days to respectively obtain the shape-controllable rod-shaped polysilsesquioxane, cluster-shaped polysilsesquioxane, three-dimensional sheet-shaped polysilsesquioxane, porous polysilsesquioxane, spherical polysilsesquioxane and blocky polysilsesquioxane.
Use of the hydrophobic shape-controllable polysilsesquioxane obtained by said method for the preparation of a hydrophobic coating.
Compared with the prior art, the preparation method and the application of the polysilsesquioxane with the controllable hydrophobic shape have the following innovations:
1. by adjusting the content of reactants and the concentration of alkali, the polysilsesquioxane can realize the regulation and control of rod-shaped, cluster-shaped, three-dimensional sheet-shaped, porous, spherical and blocky shapes;
2. the raw materials are easy to obtain, the operation is simple and convenient, and the industrial production can be realized;
3. the prepared polysilsesquioxane dispersion liquid with the controllable shape can be spin-coated on substrates made of different materials to be used as a hydrophobic coating, and has the functions of self-cleaning and corrosion prevention.
The invention relates to a preparation method of polysilsesquioxane with controllable hydrophobic shape, wherein long-chain silane is R in the reaction scheme of polysilsesquioxaneLShort-chain silanes of RS(ii) a The structural schematic of the final polysilsesquioxane is not limited to only one of the following, R being the alkyl group of a long chain silane or a short chain silane:
Figure BDA0003298925570000021
drawings
FIG. 1 is a topographical view of a shape-controllable polysilsesquioxane of the present invention wherein A: a rod shape; b: clustering; c: three-dimensional sheet shape; d: is porous; e: spherical; f: block-shaped;
FIG. 2 shows the NMR spectrum of a polysilsesquioxane of the present invention, in the case of a cluster structure, the polysilsesquioxane obtained is T2Structure ((-OSi)2(-OH) SiR), R is the alkyl group of a long chain silane or a short chain silane.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but is not limited to the following examples.
Example 1
a. Adding 50mL of ethanol into 4mL of NaOH solution with the concentration of 0.1M, uniformly mixing and stirring, and then adding 4mL of hexadecyl trimethoxy silane as long-chain silane and methyl trimethoxy silane as short-chain silane with the mass ratio of 1:5 to obtain a semitransparent solution;
b. b, performing ultrasonic treatment on the semitransparent solution obtained in the step a for 4min at room temperature to obtain an opaque solution;
c. standing and volatilizing the opaque solution obtained in the step b at room temperature for 9 days to obtain rod-shaped polysilsesquioxane with controllable shape, as shown in figure 1A;
the obtained rod-like polysilsesquioxane is used as a hydrophobic coating and is spin-coated on a substrate made of a glass sheet material, so that the hydrophobic property of the substrate material can be effectively improved, and the specific operation is as follows:
adding rod-shaped polysilsesquioxane into an ethanol solution, and performing ultrasonic dispersion for 2 hours to obtain a dispersion liquid, wherein the polysilsesquioxane accounts for 30% of the mass volume of the ethanol solution;
dripping 5 mu L of dispersion liquid on a glass sheet, rotating at 2000rpm, spin-coating for 30s, and repeating for 4 times to obtain a hydrophobic substrate;
the resulting hydrophobic substrate was allowed to evaporate on standing at room temperature and the contact angle was found to be 146.0 °.
Example 2
a. Adding 50mL of ethanol into 4mL of NaOH solution with the concentration of 0.02M, uniformly mixing and stirring, and then adding 1mL of hexadecyl trimethoxy silane as long-chain silane and propyl trimethoxy silane as short-chain silane with the mass ratio of 1:0.2 to obtain a semitransparent solution;
b. b, performing ultrasonic treatment on the semitransparent solution obtained in the step a for 10min at room temperature to obtain an opaque solution;
c. standing and volatilizing the opaque solution obtained in the step B at room temperature for 14 days to obtain clustered polysilsesquioxane, as shown in figure 1B;
the obtained clustered polysilsesquioxane is used as a hydrophobic coating and is spin-coated on a cotton cloth substrate, so that the hydrophobic property of the substrate material can be effectively improved, and the specific operation is as follows:
adding clustered polysilsesquioxane into an ethanol solution, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid, wherein the polysilsesquioxane accounts for 25% of the mass volume of the ethanol solution;
dripping 8 mu L of dispersion liquid on cotton cloth, rotating at 2500rpm, spin-coating for 20s, and repeating for 3 times to obtain a hydrophobic substrate;
the prepared hydrophobic substrate was left to volatilize at room temperature and the contact angle was measured to be 147.5 °.
Example 3
a. Adding 50mL of ethanol into 4mL of NaOH solution with the concentration of 0.02M, uniformly mixing and stirring, and adding 8mL of hexadecyl trimethoxy silane as long-chain silane and dodecyl trimethoxy silane as short-chain silane with the mass ratio of 1:1 to obtain a semitransparent solution;
b. b, performing ultrasonic treatment on the semitransparent solution obtained in the step a for 1min at room temperature to obtain an opaque solution;
c. standing the opaque solution obtained in the step b at room temperature for volatilizing for 1 day to obtain three-dimensional flaky polysilsesquioxane as shown in figure 1C;
the obtained three-dimensional flaky polysilsesquioxane is used as a hydrophobic coating and is spin-coated on a substrate made of a silicon wafer material, so that the hydrophobic property of the substrate material can be effectively improved, and the specific operation is as follows:
adding three-dimensional flaky polysilsesquioxane into an ethanol solution, and performing ultrasonic dispersion for 4 hours to obtain a dispersion liquid, wherein the polysilsesquioxane accounts for 20% of the mass volume of the ethanol solution;
dripping 10 mu L of dispersion liquid on a silicon wafer, rotating at 3000rpm, spin-coating for 20s, and repeating for 3 times to obtain a hydrophobic substrate;
the prepared hydrophobic substrate was left to volatilize at room temperature and the contact angle was measured to be 145.7 °.
Example 4
a. Adding 50mL of ethanol into 4mL of NaOH solution with the concentration of 0.5M, uniformly mixing and stirring, and adding 2mL of hexadecyl trimethoxy silane as long-chain silane and octyl trimethoxy silane as short-chain silane with the mass ratio of 1:10 to obtain a semitransparent solution;
b. b, performing ultrasonic treatment on the semitransparent solution obtained in the step a for 3min at room temperature to obtain an opaque solution;
c. standing the opaque solution obtained in step b at room temperature for 5 days to volatilize to obtain porous polysilsesquioxane, as shown in FIG. 1D;
porous polysilsesquioxane is used as a hydrophobic coating and is spin-coated on a substrate made of basalt fiber cloth, so that the hydrophobic property of the substrate material can be effectively improved, and the specific operation is as follows:
adding porous polysilsesquioxane into an ethanol solution, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid, wherein the polysilsesquioxane accounts for 27% of the mass volume of the ethanol solution;
dropwise adding 8 mu L of dispersion liquid onto basalt fiber cloth, rotating at 2300rpm, spin-coating for 26s, and repeating for 3 times to obtain a hydrophobic substrate;
the prepared hydrophobic substrate was left to volatilize at room temperature and the contact angle was measured to be 138.7 °.
Example 5
a. Adding 50mL of ethanol into 4mL of NaOH solution with the concentration of 0.2M, uniformly mixing and stirring, and then adding 4mL of hexadecyl trimethoxy silane as long-chain silane and vinyl trimethoxy silane as short-chain silane with the mass ratio of 1:8 to obtain a semitransparent solution;
b. b, performing ultrasonic treatment on the semitransparent solution obtained in the step a for 5min at room temperature to obtain an opaque solution;
c. standing the opaque solution obtained in step b at room temperature for 8 days to obtain spherical polysilsesquioxane, as shown in FIG. 1E;
spherical polysilsesquioxane is used as a hydrophobic coating and is spin-coated on a substrate made of a metal surface material, so that the hydrophobic property of the substrate material can be effectively improved, and the specific operation is carried out according to the following steps:
adding spherical polysilsesquioxane into an ethanol solution, and performing ultrasonic dispersion for 2 hours to obtain a dispersion liquid, wherein the polysilsesquioxane accounts for 22% of the mass volume of the ethanol solution;
dropwise adding 9 mu L of dispersion liquid onto the metal surface, rotating at 2600rpm, spin-coating for 24s, and repeating for 4 times to obtain a hydrophobic substrate;
the prepared hydrophobic substrate was left to volatilize at room temperature and the contact angle was measured to be 143.7 °.
Example 6
a. Adding 50mL of ethanol into 4mL of NaOH solution with the concentration of 0.4M, uniformly mixing and stirring, and adding 6mL of octadecyl trimethoxy silane and methyl trimethoxy silane in the mass ratio of 1:9 to obtain a semitransparent solution;
b. b, performing ultrasonic treatment on the semitransparent solution obtained in the step a for 5min at room temperature to obtain an opaque solution;
c. standing the opaque solution obtained in step b at room temperature for 12 days to volatilize to obtain polysilsesquioxane in bulk form, as shown in FIG. 1F;
the blocky polysilsesquioxane is used as a hydrophobic coating and is spin-coated on a substrate made of glass fiber cloth, so that the hydrophobic property of the substrate material can be effectively improved, and the method comprises the following specific operations:
adding blocky polysilsesquioxane into an ethanol solution, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid, wherein the polysilsesquioxane accounts for 30% of the mass volume of the ethanol solution;
dropwise adding 7 mu L of dispersion liquid onto glass fiber cloth, rotating at 2500rpm, spin-coating for 25s, and repeating for 3 times to obtain a hydrophobic substrate;
the prepared hydrophobic substrate was left to volatilize at room temperature and the contact angle was measured to be 142.5 °.
Example 7
a. Adding 50mL of ethanol into 4mL of NaOH solution with the concentration of 0.4M, uniformly mixing and stirring, and adding 5mL of octadecyl trimethoxy silane and vinyl trimethoxy silane in the mass ratio of 1:7 to obtain a semitransparent solution;
b. b, performing ultrasonic treatment on the semitransparent solution obtained in the step a for 6min at room temperature to obtain an opaque solution;
c. standing the opaque solution obtained in step b at room temperature for 13 days to volatilize to obtain spherical polysilsesquioxane as shown in FIG. 1E;
spherical polysilsesquioxane is used as a hydrophobic coating and is spin-coated on a substrate made of glass fiber cloth, so that the hydrophobic property of the substrate material can be effectively improved, and the specific operation is as follows:
adding spherical polysilsesquioxane into an ethanol solution, and performing ultrasonic dispersion for 2 hours to obtain a dispersion liquid, wherein the polysilsesquioxane accounts for 24% of the mass volume of the ethanol solution;
dropwise adding 5 mu L of dispersion liquid onto glass fiber cloth, rotating at 2400rpm, spin-coating for 28s, and repeating for 4 times to obtain a hydrophobic substrate;
the prepared hydrophobic substrate was left to volatilize at room temperature and the contact angle was measured to be 144.5 °.
Example 8
a. Adding 50mL of ethanol into 4mL of NaOH solution with the concentration of 0.2M, uniformly mixing and stirring, and adding 2mL of octadecyl trimethoxy silane and propyl trimethoxy silane with the mass ratio of 1:8 to obtain a semitransparent solution;
b. b, performing ultrasonic treatment on the semitransparent solution obtained in the step a for 5min at room temperature to obtain an opaque solution;
c. standing the opaque solution obtained in the step B at room temperature for volatilizing for 11 days to obtain clustered polysilsesquioxane, as shown in FIG. 1B;
the clustered polysilsesquioxane is used as a hydrophobic coating and is spin-coated on a substrate made of glass fiber cloth, so that the hydrophobic property of the substrate material can be effectively improved, and the specific operation is as follows:
adding clustered polysilsesquioxane into an ethanol solution, and performing ultrasonic dispersion for 3 hours to obtain a dispersion liquid, wherein the polysilsesquioxane accounts for 25% of the mass volume of the ethanol solution;
dropwise adding 6 mu L of dispersion liquid onto glass fiber cloth, rotating at 2700rpm, spin-coating for 24s, and repeating for 3 times to obtain a hydrophobic substrate;
the prepared hydrophobic substrate was left to volatilize at room temperature and the contact angle was measured to be 147.2 °.
Example 9
a. Adding 4mL of NaOH solution with the concentration of 0.4M into 50mL of ethanol, mixing and stirring uniformly, and then adding 5mL of octadecyl trimethoxy silane and dodecyl trimethoxy silane with the mass ratio of 1:0.1 to obtain a semitransparent solution;
b. b, performing ultrasonic treatment on the semitransparent solution obtained in the step a for 8min at room temperature to obtain an opaque solution;
c. standing the opaque solution obtained in the step b at room temperature for volatilizing for 14 days to obtain three-dimensional flaky polysilsesquioxane as shown in figure 1C;
the three-dimensional flaky polysilsesquioxane is used as a hydrophobic coating and is spin-coated on a substrate made of glass fiber cloth, so that the hydrophobic property of the substrate material can be effectively improved, and the specific operation is as follows:
adding three-dimensional flaky polysilsesquioxane into an ethanol solution, and performing ultrasonic dispersion for 2 hours to obtain a dispersion liquid, wherein the polysilsesquioxane accounts for 10% of the mass volume of the ethanol solution;
dropwise adding 8 mu L of dispersion liquid onto glass fiber cloth, rotating at 2800rpm, spin-coating for 20s, and repeating for 5 times to obtain a hydrophobic substrate;
the prepared hydrophobic substrate was left to volatilize at room temperature and the contact angle was measured to be 146.5 °.
Example 10
a. Adding 4mL of NaOH solution with the concentration of 0.5M into 50mL of ethanol, mixing and stirring uniformly, and then adding 1mL of octadecyl trimethoxy silane and octyl trimethoxy silane with the mass ratio of 1:10 to obtain a semitransparent solution;
b. b, performing ultrasonic treatment on the semitransparent solution obtained in the step a for 4min at room temperature to obtain an opaque solution;
c. standing the opaque solution obtained in step b at room temperature for volatilizing for 10 days to obtain porous polysilsesquioxane, as shown in FIG. 1D;
the porous polysilsesquioxane can be used as a hydrophobic coating and is spin-coated on a substrate made of glass fiber cloth, so that the hydrophobic property of the substrate material can be effectively improved, and the specific operation is as follows:
adding porous polysilsesquioxane into an ethanol solution, and performing ultrasonic dispersion for 4 hours to obtain a dispersion liquid, wherein the polysilsesquioxane accounts for 28% of the mass volume of the ethanol solution;
dripping 6 mu L of dispersion liquid on glass fiber cloth, rotating at 2500rpm, spin-coating for 25s, and repeating for 3 times to obtain a hydrophobic substrate;
the prepared hydrophobic substrate was left to volatilize at room temperature and the contact angle was measured to be 142.7 °.

Claims (2)

1. A preparation method of polysilsesquioxane with controllable hydrophobic shape is characterized by comprising the following steps:
a. adding 50mL of ethanol into 4mL of NaOH solution with the concentration of 0.02-0.5M, mixing and stirring uniformly, and adding 0.5-8mL of long-chain silane and short-chain silane with the mass ratio of 1:0.1-10 to obtain a semitransparent solution, wherein the long-chain silane comprises hexadecyl trimethoxy silane or octadecyl trimethoxy silane; short chain silanes include methyltrimethoxysilane, vinyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, or dodecyltrimethoxysilane;
b. b, performing ultrasonic treatment on the semitransparent solution obtained in the step a for 1-10min at room temperature to obtain an opaque solution;
c. and c, standing and volatilizing the opaque solution obtained in the step b at room temperature for 1-14 days to respectively obtain the shape-controllable rod-shaped polysilsesquioxane, cluster-shaped polysilsesquioxane, three-dimensional sheet-shaped polysilsesquioxane, porous polysilsesquioxane, spherical polysilsesquioxane and blocky polysilsesquioxane.
2. Use of a hydrophobic shape-controllable polysilsesquioxane obtained by a process as claimed in claim 1 for the preparation of a hydrophobic coating.
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